CN1765490A - Catalyst for C12-C12 fat carboxylic acid ketonization and its application - Google Patents
Catalyst for C12-C12 fat carboxylic acid ketonization and its application Download PDFInfo
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- CN1765490A CN1765490A CN 200510114257 CN200510114257A CN1765490A CN 1765490 A CN1765490 A CN 1765490A CN 200510114257 CN200510114257 CN 200510114257 CN 200510114257 A CN200510114257 A CN 200510114257A CN 1765490 A CN1765490 A CN 1765490A
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Abstract
The invention provides a C2-C12 aliphatic carboxylic acid ketone activator. The invention uses gamma-aluminum oxide as carrier and the single, double elements, and ternary elements of lanthanum, cerium, praseodymium and neodymium of light lanthanide series rare earth as active components. While the activating carrier method comprises (1) the heat treatment process while the treatment temperature is 480-800 Deg. C; (2) azotic acid aqueous solution method while the concentration of azotic acid aqueous solution is 5-45%; (3) evacuation method. In addition, the activator is prepared via the immersion method while it can be used to C2-C12 aliphatic carboxylic acid ketone.
Description
Technical field
The present invention relates to a kind of fat carboxylic acid ketonization catalyst, preparation method and application thereof, particularly a kind of C
2-C
12Fat carboxylic acid ketonization Catalysts and its preparation method and application.。
Background technology
Acid-acid system is one of alkenolic important method of preparation under hot conditions.The employed catalyst of acid-acid system is a carrier supported metal oxide.
EP0085996 adopts the synthetic asymmetric aliphatic ketone of rare earth metal/aluminium oxide catalyst, and active component is the binary oxide of didymum, and carrier is not done any processing.Because of its activity is low, so the method for the simple ketone of taking to circulate improves the selectivity of unsymmetrical ketone; After the methyl alcohol absorption product, the mass percent of the methyl isopropyl Ketone in the circulation products is 83.9%.
US 4,528,400 and US 4,570,021 proposed to adopt the method for the synthetic ketone of alumina load cerium oxide catalyst.US 5,001, and 273 adopt CeO
2/ Al
2O
3Catalyst synthesizes asymmetric aliphatic ketone.The result shows CeO
2/ Al
2O
3The low temperature active of series catalysts is low, the reaction temperature height, but carbon accumulation resisting ability is strong, and the life cycle of catalyst is short.
US 4,754, and 074 has proposed a kind of method that adopts the synthetic dialkyl ketone of alumina load manganese oxide catalysis.US 4,950, and 763 adopt the synthetic ketone of the titanium oxide catalysis that contains one or more metal oxides; Metal oxide is first, second main group metal, as lithium, sodium, potassium, or rare earth metal, as lanthanum and cerium.US6,265,618 are a kind of method that adopts the synthetic ketone of niobium catalytic, are specially adapted to synthetic cyclopropyl ketone.The specific activity of the low temperature of foregoing invention is higher, and the life-span is hundreds of hour only, not industrialization.
China's acid-acid system synthctic fat ketone catalyst is mainly used in acetate and isobutyric acid synthesizing methyl nezukone and acetate and n-butyric acie Synthetic 2-pentanone.A kind of catalyst is the oxide that adopts alumina load La, Nd, Pr, and in catalyst preparation process, carrier does not carry out activation processing; This kind catalyst inner surface is acid big; When using on the methyl isopropyl Ketone process units, service life is less than 720 hours, reaction temperature 440-460 ℃.Another kind of catalyst adopts the oxide of titania oxide supported La, Nd, Pr, and initial activity and selectivity are all high; When the methyl isopropyl Ketone process units is used, because TiO
2Intensity difference, catalyst life only has 500 hours; Catalyst is raw material with the mixed chlorinated rare earth, because rare earth is the mixture of multiple rare earth, and the ketonize reaction temperature height of catalyst, active low, life-span weak point; In catalyst preparation process, also can emit a large amount of hydrogen chloride and nitrogen oxide, contaminated environment not only, and require high to the material of production equipment.At present, in methyl isopropyl Ketone was produced, the acetate conversion ratio was 96.5%; The isobutyric acid conversion ratio is 95.5%; Selectivity with the MIPK of Acetometer is 39.7%, and reaction temperature is generally 440-465 ℃.The subject matter that prior art exists is that reaction temperature height, material carbon distribution are serious, catalyst service life is short, energy consumption and material consumption are higher.
Summary of the invention
The objective of the invention is to solve the ketonize reaction temperature height of acid-acid system synthctic fat ketone, carbon distribution is serious, the service life of catalyst is short, and energy consumption and the high problem of material consumption, invented a kind of new catalyst, and be applied to the ketonize reaction of ester fat ketone, to reduce the ketonize reaction temperature, improve the carbon accumulation resisting ability of catalyst, prolong catalyst service life.
Technical scheme of the present invention is to realize like this.
C provided by the invention
2-C
12The fat carboxylic acid ketonization catalyst is to be carrier with the gama-alumina, and the mass percent of the gama-alumina in the carrier is 99.5-99.9%; Its active component is:
(A) oxide of lanthanum is as the monobasic active component, and its content is the 1-34% of catalyst quality; Or
(B) oxide of cerium is as the monobasic active component, and its content is the 5-35% of catalyst quality; Or
(C) oxide of praseodymium is as the monobasic active component, and its content is the 5-45% of catalyst quality; Or
(D) binary complex of the oxide of praseodymium, cerium is an active component, and its content is the 5-40% of catalyst quality, and wherein the mol ratio of praseodymium and cerium is 1: 0.1-30; Or
(E) binary complex of the oxide of neodymium, cerium is an active component, and its content is the 1-50% of catalyst quality, and wherein the mol ratio of neodymium and cerium is 0.1-30: 1; Or
(F) ternary complex of the oxide of cerium, praseodymium, neodymium is an active component, and its content is the 0.5-50% of catalyst quality, wherein praseodymium: neodymium: the mol ratio of cerium is 0.1-23: 0.1-30: 1-30.
The present invention adopts the oxide of cerium, lanthanum, neodymium or praseodymium to form the activity of such catalysts component.Cerium wherein can suppress aliphatic acid and alkenolic coking and carbonization, improves selection of catalysts, prolongs life of catalyst; Lanthanum, neodymium or praseodymium can improve the activity of aliphatic acid ketonize low-temperature zone.
The present invention is through a large amount of tests, and having selected specific area is 120-350m
2The gama-alumina of/g is a carrier, and has adopted special method that carrier has been carried out activation processing.The activating treatment method of three kinds of carriers is: aqueous solution of nitric acid is washed method, roasting method and vacuum method.
Carrier activation method 1: gama-alumina is carried out acidifying with 5-45% nitric acid, and souring temperature is 5-65 ℃, acidificatoin time 0.5-48h, dry, bake out temperature 100-130 ℃, drying time is 2-60h, carry out roasting again, sintering temperature 450-700 ℃, roasting time is 2-8h.Carrier can reduce the composition that is dissolved by acid of carrier by acidification, increases the stability of catalyst.
Carrier activation method 2: the roasting gama-alumina, sintering temperature 450-800 ℃, roasting time is 1-20h.Carrier can improve the pore structure of carrier and the acidity of inner surface by calcination process.
Carrier activation method 3: gama-alumina is dried, and bake out temperature 100-130 ℃, drying time is 2-60h, more dried gama-alumina is placed the container of sealing, vacuumizes with vavuum pump.By the vacuum activation, can reduce the gas content of micropore in the carrier, improve adsorption capacity to maceration extract, active constituent is evenly distributed.
Preparation of catalysts method provided by the invention is: the carrier after will activating floods with the nitrate solution of active constituent, and dip time is 1-60h, separates and soaks surplus liquid, carries out drying and high-temperature roasting, makes catalyst.
For example, with commercially available neodymia and salpeter solution reaction, constantly stir earlier, neodymia is dissolved fully, adjusting PH is 3～6; Praseodymium oxide and salpeter solution are constantly stirred, and it is 3～6 that consoluet solution is adjusted PH; Directly dissolve cerous nitrate in the water, be mixed with cerous nitrate solution, with various single rare earth nitrate solutions proportionally, be re-dubbed the ternary maceration extract, maceration extract and the carrier of handling well are carried out excessive dipping, flooded 1-60 hour, separate and soak surplus liquid, descended dry 4-10 hour at 110-120 ℃, at 500-800 ℃ of roasting 4-8 hour, naturally be cooled to room temperature, make finished catalyst.
Ketonize catalyst of the present invention can be applied to C
2-C
12The fat carboxylic acid ketonization reaction generates C
3-C
13Aliphatic ketone.C
3-C
13Aliphatic ketone comprises straight chain and side chain aliphatic ketone.Reaction raw materials is C
2-C
12The mixture of aliphatic carboxylic acid, acetate and water, C
2-C
12The mol ratio of aliphatic carboxylic acid, acetate and water is 0.8-2.0: 1.0-3.0: 2-5.The vapourizing temperature 120-350 of raw material ℃, the air speed of aliphatic carboxylic acid is 0.35-1.5h
-1, 350 ℃-500 ℃ of reaction temperatures, reaction unit is fixed bed reactors.
Added water in the ketonize reaction raw materials of the present invention, can suppress aliphatic acid, prolonged life of catalyst in high-temperature-coked and carbonization.
Catalyst of the present invention is used for C
2-C
12Aliphatic carboxylic acid decarboxylation ketonize, C
2-C
12Aliphatic carboxylic acid refers in particular to one of propionic acid, isobutyric acid, n-butyric acie, positive enanthic acid, n-caproic acid, pivalic acid or dodecoic acid, as acetate and isobutyric acid synthesizing methyl nezukone, acetate and n-butyric acie Synthetic 2-pentanone, acetate and propionic acid synthesize butanone, acetate and n-caproic acid Synthetic 2-heptanone, acetate and positive enanthic acid Synthetic 2-octanone, synthetic 3, the 3-dimethyl-2-butanone of acetate and pivalic acid, acetate and positive dodecoic acid Synthetic 2-ten triketone, these ketone are the methyl aliphatic ketone, also are unsymmetrical ketone; Acetate and acetate synthesize acetone, and propionic acid and propionic acid synthesize propione; Acetone, propione are symmetrical aliphatic ketone, and methyl isopropyl Ketone and 3,3-dimethyl-2-butanone are the aliphatic ketone of side chain.Reaction raw materials gasifies through vaporizer, and vapourizing temperature 120-350 ℃, enter the reactor that makes catalyst is housed, carry out the ketonize reaction, reaction temperature 350-500 ℃, reaction pressure 0.01-0.5MPa, the air speed 0.35-1.5h of total acid
-1, carry out condensation and cooling through condenser, be layered as oil phase and water.Oil phase obtains corresponding aliphatic ketone through rectifying.
Preparation of Catalyst methyl isopropyl Ketone, 2 pentanone, butanone, methyln-hexyl ketone, 2-heptanone, 3,3-dimethyl-2-butanone or 2-ten triketones that provided preferably are provided in the present invention.
Carrier provided by the invention is commercially available activated alumina, and the pore structure characteristic that mercury injection method is measured carrier is as follows:
Pore volume 0.3-0.8ml/g
Specific area: 120-350m
2/ g
It is gama-alumina that the X-diffraction approach is measured the carrier crystalline structure
The physical and chemical performance that fat carboxylic acid ketonization catalyst provided by the invention is measured with mercury injection method is as follows:
Pore volume: 0.3-0.7ml/g
Specific area: 150-300m
2/ g
Catalyst provided by the invention can be used for the ketonize of aliphatic acid, is particularly useful for C
2-C
12Aliphatic carboxylic acid is as the ketonize of acetate, propionic acid, n-butyric acie, isobutyric acid, pivalic acid, enanthic acid, sad or dodecoic acid.Because carrier through carrier activation method provided by the invention, has improved the pore structure of carrier and the acid-base value of inner surface, make the activity of such catalysts center rationally, stablize, be evenly distributed on the catalyst inner surface.
It is the catalyst of active component that the present invention preferably adopts the ternary complex of the oxide of cerium, praseodymium, neodymium.The introducing of cerium can suppress aliphatic acid and alkenolic coking and carbonization; The introducing of praseodymium can improve the activity of aliphatic acid ketonize low-temperature zone, reduces reaction temperature, and anti-carbon deposition ability is strong.
When catalyst provided by the invention was used for the ketonize of aliphatic acid, generally with the increase of carbon number, its ketonize temperature also improves, and was lower than the catalyst ketonize temperature of other patent.For example, acetate ketonize temperature is 350-400 ℃, propionic acid ketonize temperature is 370-410 ℃, acetate and different (just) butyric acid ketonize temperature are 390-450 ℃, enanthic acid and acetate ketonize temperature are 420-460 ℃, sad and acetate ketonize temperature is 450-490 ℃, and acetate and pivalic acid ketonize temperature are 390-460 ℃, and acetate and dodecoic acid ketonize temperature are 450-500 ℃.
C provided by the invention
2-C
12The fat carboxylic acid ketonization catalyst compared with prior art has following advantage:
1, the present invention with cerium or praseodymium as the activity of such catalysts component, can suppress aliphatic acid and alkenolic coking and carbonization, improve the activity of aliphatic acid ketonize low-temperature zone, reduce reaction temperature, activity and selectivity are higher, anti-carbon deposition ability is strong, and catalyst life is long, is specially adapted to calandria type fixed bed acid-sour ketonize technology.
2, catalyst provided by the invention has microporous structures such as suitable specific area, pore volume, pore-size distribution, and active material can evenly distribute at the catalyst inner surface, can improve performance indications such as activity of such catalysts, selectivity.
3, the ketonize technological operation is simple, and reaction temperature is lower.
4, the present invention has carried out activation processing with special method to carrier, reduced the composition that is dissolved by acid of carrier, increased the stability of catalyst, the pore structure of carrier and the acidity of carrier inner surface have been improved, increased the distributing homogeneity of active material, thereby improved catalyst activity, selectivity and anti-carbon deposit at the catalyst inner surface.
5,, thereby reduced energy consumption because catalyst provided by the invention can reduce reaction temperature; Strong because of this catalyst anti-carbon deposition ability simultaneously, therefore can prolong the service life of catalyst, and then reduce production costs.
Description of drawings
Fig. 1 is the ESEM phenogram of carrier;
The ESEM phenogram of Fig. 2 catalyst.
The specific embodiment
The appearance that the catalyst usefulness electronics ESEM that the present invention makes characterizes as shown in Figure 1 and Figure 2;
Now in conjunction with the embodiments the present invention is described in detail.
(1) preparation of carrier: in an acid-resistant container, salpeter solution (the nitric acid that adds distilled water and 75% (mass percent) successively, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows), preparation 18-20% dilute nitric acid solution 1000ml is with the gama-alumina (alundum (Al of 800g, the Tianjin Chemical Research ﹠ Desing Inst product, as follows) join above-mentioned dilute nitric acid solution, constantly stirring gently continues 10 hours, separation of oxygenated aluminium and dilute nitric acid solution, aluminium oxide is placed acidproof dish, through under 115 ℃ of temperature, dry 6 hours, under 500 ℃, roasting 4 hours, cooling makes carrier A naturally.
(2) preparation of maceration extract: in an acid-resistant container, add purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) distilled water of 100g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 75% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 4.5, adding distil water makes neodymium nitrate solution to 500ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 100g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 75% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ praseodymium oxide dissolves fully, and control PH is 4.5, adding distil water makes praseodymium nitrate solution to 500ml again.Contain the every 1000ml cerous nitrate solution of 200g cerium oxide with 99.5% cerous nitrate (cerous nitrate, the product of Baotou rare earth three factories, as follows) and distilled water preparation.Is to mix at 1: 0.5: 0.8 the praseodymium nitrate solution, neodymium nitrate solution and the cerous nitrate solution that make according to volume ratio, stirs.Make maceration extract A.Carrying out 1.5 times of volumes and carry out the excess volume dipping making carrier A and the maceration extract A that makes, flood 6 hours, separate the surplus liquid of dipping, is under 115 ℃ in temperature, and dry 4 hours is roasting 4 hours under 560 ℃ of conditions in temperature, cools off naturally, makes catalyst A.
(3) evaluation of catalyst: isobutyric acid (isobutyric acid with 99.2%, Jilin Petrochemical chemical fertilizer factory product, as follows) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass percent are 40%: 40%: 20%, are 350 ℃ of vaporizations down in temperature, under 420 ℃, 0.1Mpa condition, react the air speed 0.5h of acetate and isobutyric total acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography, table 1 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 2
(1) preparation of carrier: with dry 6 hours (baking temperature is 115 ℃) of γ-activated alumina of 200g (alundum (Al, Tianjin Chemical Research ﹠ Desing Inst product, as follows), under 750 ℃, roasting 4 hours is lowered the temperature naturally, makes carrier B.
(2) preparation of maceration extract: in an acid-resistant container, add purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) distilled water of 200g and 200ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 75% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 3.1, adding distil water makes neodymium nitrate solution to 800ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 200g and 200ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 75% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 3.9, adding distil water makes praseodymium nitrate solution to 800ml again.Contain the every 1000ml cerous nitrate solution of 250g cerium oxide with 99.5% cerous nitrate (cerous nitrate, the product of Baotou rare earth three factories, as follows) and distilled water preparation.Is to mix at 1: 0.8: 1.2 the praseodymium nitrate solution, neodymium nitrate solution and the cerous nitrate solution that make according to volume ratio, stirs.Make maceration extract B.The maceration extract B that makes carrier B and make being carried out 1.5 times of volumes carry out the excess volume dipping, flooded 10 hours, separate the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, is 580 ℃ in temperature and carried out roasting 4 hours that cooling makes catalyst B naturally.
(3) evaluation of catalyst: isobutyric acid (isobutyric acid with 99.2%, Jilin Petrochemical chemical fertilizer factory product, as follows) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass percent are 38%: 39%: 23%, in temperature is 350 ℃ of vaporizations down, in temperature is under 420 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of acetate and isobutyric total acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography.Table 2 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 3
Preparing carriers: according to the carrier B preparation method, preparation 200g support C.
(2) preparation of maceration extract: in an acid-resistant container, add purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) distilled water of 100g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 3.0, adding distil water makes neodymium nitrate solution to 500ml again.Contain the every 500ml cerous nitrate solution of 100g cerium oxide with 99.5% cerous nitrate (cerous nitrate, the product of Baotou rare earth three factories, as follows) and distilled water configuration.Is to mix at 1: 1.2 the neodymium nitrate solution that makes and cerous nitrate solution according to volume ratio, stirs.Make maceration extract C.The maceration extract C that makes support C and make being carried out 1.3 times of volumes carry out the excess volume dipping, flooded 8 hours, separate the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, is 560 ℃ in temperature and carried out roasting 4 hours that cooling makes catalyst C naturally
(3) evaluation of catalyst: 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass percent is 8%1: 19%, is 270 ℃ of vaporizations down in temperature, is under 370 ℃ in temperature, pressure is that 0.1MPa reacts, the air speed 0.55h of acetate
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out complete analysis respectively with gas-chromatography.Table 3 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
(1) preparing carriers: with the gama-alumina of 200g, specific area is 300m
2/ g (alundum (Al, Wenzhou alumina producer product, below different) through under 115 ℃ of temperature, dry 6 hours, under 750 ℃, roasting 4 hours was lowered the temperature naturally, makes carrier D.
(2) preparation of maceration extract: in an acid-resistant container, add purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) distilled water of 100g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 2.9, adding distil water makes neodymium nitrate solution to 500ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 100g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 75% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ praseodymium oxide dissolves fully, and control PH is 2, adding distil water makes praseodymium nitrate solution to 500ml again.Contain the every 500ml cerous nitrate solution of 100g cerium oxide with 99.5% cerous nitrate (cerous nitrate, the product of Baotou rare earth three factories, as follows) and distilled water preparation.Is to mix at 0.5: 0.5: 1.2 the neodymium nitrate solution, praseodymium nitrate solution and the cerous nitrate solution that make according to volume ratio, stirs.Make maceration extract D.The maceration extract D that makes carrier D and make being carried out 1.5 times of volumes carry out the excess volume dipping, flooded 6 hours, separate the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, is 560 ℃ in temperature and carried out roasting 4 hours that cooling makes catalyst D naturally.
(3) evaluation of catalyst: caprylic acid (caprylic acid with 99.2%, Jinshi City recovery fine chemistry industry research institute, following difference) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product, as follows) and distilled water, preparation raw material, mol ratio is 1: 1.5: 2, is 350 ℃ of vaporizations down in temperature, is under 450 ℃ in temperature, pressure is that 0.1MPa reacts, the air speed 0.6h of the total acid of acetate and caprylic acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography, table 4 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 5
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier E.
(2) preparation of maceration extract: in an acid-resistant container, add purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) distilled water of 75g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 75% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 3.5, adding distil water makes neodymium nitrate solution to 500ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 200g and 200ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 75% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ praseodymium oxide dissolves fully, and control PH is 4.5, adding distil water makes praseodymium nitrate solution to 800ml again.Contain the every 1000ml cerous nitrate solution of 150g cerium oxide with 99.5% cerous nitrate (cerous nitrate, the product of Baotou rare earth three factories, as follows) and distilled water preparation.Is to mix at 1: 1: 0.5 the praseodymium nitrate solution, neodymium nitrate solution and the cerous nitrate solution that make according to volume ratio, stirs.Make maceration extract E.The maceration extract E that makes carrier E and make being carried out 1.5 times of volumes carry out the excess volume dipping, flooded 6 hours, separate the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, is 560 ℃ in temperature and carried out roasting 4 hours that cooling makes catalyst E naturally.
(3) catalyst activity evaluation: isobutyric acid (isobutyric acid with 99.2%, Jilin Petrochemical chemical fertilizer factory product, as follows) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass percent are 38%: 39%: 23%, in temperature is 350 ℃ of vaporizations down, in temperature is under 420 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of acetate and isobutyric total acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography.Table 5 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 6
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier F.
(2) preparation of maceration extract: in an acid-resistant container, add purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) distilled water of 100g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 3.5, adding distil water makes neodymium nitrate solution to 500ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 100g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 4.5, adding distil water makes praseodymium nitrate solution to 500ml again.Contain the every 1000ml cerous nitrate solution of 200g cerium oxide with 99.5% cerous nitrate (cerous nitrate, the product of Baotou rare earth three factories, as follows) and distilled water preparation.Is to mix at 1: 1: 2 the praseodymium nitrate solution, neodymium nitrate solution and the cerous nitrate solution that make according to volume ratio, stirs.Make maceration extract F.The maceration extract F that makes carrier F and make being carried out 1.5 times of volumes carry out the excess volume dipping, flooded 6 hours, separate the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, is 560 ℃ in temperature and carried out roasting 4 hours that cooling makes catalyst F naturally.
(3) catalyst activity evaluation: isobutyric acid (isobutyric acid with 99.2%, Jilin Petrochemical chemical fertilizer factory product, as follows) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass percent are 38%: 39%: 23%, in temperature is 350 ℃ of vaporizations down, in temperature is under 420 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of acetate and isobutyric total acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography.Table 5 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 7
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier G.
(2) preparation of maceration extract: in an acid-resistant container, add purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) distilled water of 150g and 200ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 3.5, adding distil water makes neodymium nitrate solution to 500ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 150g and 200ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 4.5, adding distil water makes praseodymium nitrate solution to 500ml again.Contain the every 1000ml cerous nitrate solution of 300g cerium oxide with 99.5% cerous nitrate (cerous nitrate, the product of Baotou rare earth three factories, as follows) and distilled water preparation.Is to mix at 1: 1: 1 the praseodymium nitrate solution, neodymium nitrate solution and the cerous nitrate solution that make according to volume ratio, stirs.Make maceration extract G.The maceration extract G that makes carrier G and make being carried out 1.5 times of volumes carry out the excess volume dipping, flooded 6 hours, separate the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, is 560 ℃ in temperature and carried out roasting 4 hours that cooling makes catalyst G naturally.
(3) catalyst activity evaluation: isobutyric acid (isobutyric acid with 99.2%, Jilin Petrochemical chemical fertilizer factory product, as follows) and 95% (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass percent are 38%: 39%: 23%, in temperature is 350 ℃ of vaporizations down, in temperature is under 420 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of acetate and isobutyric total acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography, table 5 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 8
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier H
(2) Preparation of catalysts: according to catalyst G preparation method, preparation 200g catalyst H
(3) catalyst activity evaluation: n-butyric acie (n-butyric acie with 99.2%, Shandong, Shandong two factory's products, following difference) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass ratio is 38%: 39%: 23%, in temperature is 350 ℃ of vaporizations down, in temperature is under 420 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of the total acid of acetate and n-butyric acie
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out complete analysis respectively with gas-chromatography, table 6 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 9
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier I.
(2) Preparation of catalysts: according to catalyst G preparation method, preparation 200g catalyst I.
(3) catalyst activity evaluation: propionic acid (propionic acid with 99.2%, Jinshi City recovery fine chemistry industry research institute product, as follows) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mol ratio are 1: 1.2: 2.5, in temperature is 350 ℃ of vaporizations down, in temperature is under 420 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of the total acid of acetate and propionic acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography.Table 7 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 10
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier J.
(2) Preparation of catalysts: according to catalyst G preparation method, preparation 200g catalyst J.
(3) catalyst activity evaluation: (the positive enanthic acid of the positive enanthic acid with 99.0%, Tianjin recovery fine chemistry industry research institute, following difference) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mol ratio are 1: 1.2: 2.5, in temperature is 380 ℃ of vaporizations down, in temperature is under 450 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of the total acid of acetate and positive enanthic acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography, table 8 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 11
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier J.
(2) Preparation of catalysts: according to catalyst G preparation method, preparation 200g catalyst J.
(3) catalyst activity evaluation: pivalic acid (pivalic acid with 99.0%, Shandong, Shandong two factory's products, following difference) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mol ratio are 1: 1.2: 2.5, in temperature is 380 ℃ of vaporizations down, in temperature is under 440 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of the total acid of acetate and pivalic acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography.Table 9 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 12
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier J.
(2) Preparation of catalysts: according to catalyst G preparation method, preparation 200g catalyst J.
(3) catalyst activity evaluation: dodecoic acid (dodecoic acid with 99.0%, following difference) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mol ratio is 1: 1.2: 2.5, is 380 ℃ of vaporizations down in temperature, is under 440 ℃ in temperature, pressure is that 0.1MPa reacts, the air speed 0.6h of the total acid of acetate and dodecoic acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography.Table 10 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Embodiment 13
(1) preparing carriers: according to the carrier B preparation method, preparation 200g carrier K
(2) preparation of maceration extract: in an acid-resistant container, add purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) distilled water of 75g and 100ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ neodymia dissolves fully, and control PH is 3.5, adding distil water makes neodymium nitrate solution to 500ml again.Make maceration extract K.The maceration extract H that makes carrier K and make being carried out 1.5 times of volumes carry out the excess volume dipping, flooded 6 hours, separate the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, is 560 ℃ in temperature and carried out roasting 4 hours that cooling makes catalyst K naturally.
(3) catalyst activity evaluation: isobutyric acid (isobutyric acid with 99.2%, Jilin Petrochemical chemical fertilizer factory product, as follows) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass percent are 38%: 39%: 23%, in temperature is 350 ℃ of vaporizations down, in temperature is under 420 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of acetate and isobutyric total acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography.Table 11 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Comparative Examples 1
Prepare catalyst according to the EP0085996 method.
(1) carrier: specific area is 125m
2/ g, γ-Al
2O
3200g
(2) preparation of maceration extract: the distilled water that adds purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) 280g and 200ml, stir, make slip, slowly add the salpeter solution (nitric acid of 63% (mass percent) again, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows), constantly stir, the control reaction temperature is less than 65 ℃, treat that neodymia dissolves fully, control PH is 3.5, and adding distil water makes neodymium nitrate solution to 500ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 280g and 200ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ praseodymium oxide dissolves fully, and control PH is 4.5, adding distil water makes praseodymium nitrate solution to 500ml again.With the mixed liquor of two kinds of solution, be maceration extract contrasting fluid A according to 1: 1 (mass ratio).This carrier with qualified flooding 6 hours than liquid A, is separated the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, and be 560 ℃ in temperature and carried out roasting 4 hours, cooling naturally, it is right to make comparative catalyst A.
(3) catalyst activity evaluation: isobutyric acid (isobutyric acid with 99.2%, Jilin Petrochemical chemical fertilizer factory product, as follows) and 95% acetate (acetate, Jilin Petrochemical calcium carbide factory product is as follows) and distilled water, preparation raw material, mass ratio is 38%: 39%: 23%, in temperature is 350 ℃ of vaporizations down, in temperature is under 430 ℃ and 460 ℃, and pressure is that 0.1MPa reacts, the air speed 0.6h of acetate and isobutyric total acid
-1, through condensation and cooling, be divided into oil phase, water and gas phase, carry out full proximate analysis respectively with gas-chromatography, the composition of the conversion ratio of catalyst, selectivity, catalyst, reaction temperature and reaction pressure example are in table 13.
Comparative Examples 2
Prepare catalyst according to the EP0085996 method.
(1) carrier: specific area is 125m2/g, γ-Al
2O
3200g.
(2) preparation of maceration extract: the distilled water that adds purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) 220g and 200ml, stir, make slip, slowly add the salpeter solution (nitric acid of 63% (mass percent) again, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows), constantly stir, the control reaction temperature is less than 65 ℃, treat that neodymia dissolves fully, control PH is 3.5, and adding distil water makes neodymium nitrate solution to 500ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 200g and 200ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ praseodymium oxide dissolves fully, and control PH is 4.5, adding distil water makes praseodymium nitrate solution to 500ml again.With the mixed liquor of two kinds of solution, be maceration extract contrasting fluid A according to 1: 1 (mass ratio).This carrier being flooded 6 hours with qualified contrasting fluid A, separate the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, and be 560 ℃ in temperature and carried out roasting 4 hours, cooling naturally, it is right to make comparative catalyst B.
(3) catalyst activity evaluation: adopt Comparative Examples 1 with the method evaluation, table 12 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Comparative Examples 3
Prepare catalyst according to the EP0085996 method.
(1) carrier: specific area is 125m
2/ g, γ-Al
2O
3200g
(2) preparation of maceration extract: the distilled water that adds purity successively and be 99.5% neodymia (neodymia, Gansu rare earth Co., Ltd product, as follows) 180g and 200ml, stir, make slip, slowly add the salpeter solution (nitric acid of 63% (mass percent) again, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows), constantly stir, the control reaction temperature is less than 65 ℃, treat that neodymia dissolves fully, control PH is 3.5, and adding distil water makes neodymium nitrate solution to 500ml again.In an acid-resistant container, add purity successively and be 99.5% praseodymium oxide (praseodymium oxide, Gansu rare earth Co., Ltd product, as follows) distilled water of 180g and 200ml, stir, make slip, the salpeter solution (nitric acid, Jilin Petrochemical chemical fertilizer factory intermediate products, as follows) that slowly adds 63% (mass percent) again, constantly stir, the control reaction temperature treats that less than 65 ℃ praseodymium oxide dissolves fully, and control PH is 4.5, adding distil water makes praseodymium nitrate solution to 500ml again.With the mixed liquor of two kinds of solution, be maceration extract contrasting fluid A according to 1: 1 (mass ratio).This carrier with qualified flooding 6 hours than liquid A, is separated the surplus liquid of dipping, is under 115 ℃ in temperature, dry 4 hours, and be 560 ℃ in temperature and carried out roasting 4 hours, cooling naturally, it is right to make comparative catalyst C.
(3) catalyst activity evaluation: adopt Comparative Examples 1 with the method evaluation, table 12 is conversion ratio, selectivity, catalyst composition, reaction temperature and the reaction pressure of this catalyst.
Table 1
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | Methyl isopropyl Ketone selectivity % | Catalyst is formed | |||
| Acetate | Isobutyric acid | Acetate | Isobutyric acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||||
| Catalyst A | 0.5 | 420 | 0.1 | 99.94 | 98.6 | 39.5 | 64.2 | 18 | 1∶0.5∶0.8 |
| 0.7 | 450 | 0.1 | 99.95 | 99.1 | 40.2 | 68.7 | 18 | 1∶0.5∶0.8 | |
Table 2
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | Methyl isopropyl Ketone selectivity % | Catalyst is formed | |||
| Acetate | Isobutyric acid | Acetate | Isobutyric acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||||
| Catalyst B | 0.6 | 420 | 0.1 | 99.95 | 99.5 | 40.5 | 69.2 | 20.6 | 1∶0.7∶1.15 |
| 1.0 | 450 | 0.1 | 99.97 | 99.1 | 40.2 | 69.7 | 20.6 | 1∶0.7∶1.15 | |
Table 3
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | Acetone selectivity % | Catalyst is formed | |
| Total rare earth (TRE) mass content % | Neodymium: cerium (mol ratio) | ||||||
| Catalyst C | 0.55 | 370 | 0.1 | 95.81 | 98.7 | 20.6 | 1∶1.13 |
| 0.85 | 420 | 0.1 | 99.97 | 95.6 | 20.6 | 1∶1.13 | |
Table 4
Table 5
| Catalyst | Air speed h -1 | Reaction temperature | Reaction pressure | Conversion ratio % | Methyl n-heptyl ketone selectivity % | Catalyst is formed |
| ℃ | MPa | Acetate | Caprylic acid | Acetate | Caprylic acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||
| Catalyst D | 0.6 | 450 | 0.1 | 99.95 | 95.9 | 40.3 | 70.2 | 11.6 | 0.5∶0.5∶1.15 |
| 1.0 | 480 | 0.1 | 99.97 | 98.1 | 40.2 | 68.6 | 11.6 | 0.5∶0.5∶1.15 |
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | Methyl isopropyl Ketone selectivity % | Catalyst is formed | |||
| Acetate | Isobutyric acid | Acetate | Isobutyric acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||||
| Catalyst E | 0.6 | 400 | 0.1 | 98.63 | 95.9 | 38.65 | 63.2 | 8.6 | 1∶1∶0.45 |
| 0.6 | 450 | 0.1 | 99.97 | 98.1 | 41.2 | 74.6 | 8.6 | 1∶1∶0.45 | |
| Catalyst F | 0.6 | 400 | 0.1 | 97.68 | 94.3 | 37.9 | 64.2 | 8.6 | 1∶1∶1.6 |
| 0.6 | 450 | 0.1 | 99.99 | 99.16 | 41.5 | 74.9 | 8.6 | 1∶1∶1.6 | |
| Catalyst G | 0.6 | 400 | 0.1 | 98.98 | 95.3 | 38.09 | 63.86 | 8.6 | 1∶1∶0.9 |
| 0.6 | 450 | 0.1 | 99.99 | 99.6 | 40.99 | 73.7 | 8.6 | 1∶1∶0.9 | |
Table 6
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | 2 pentanone selectivity % | Catalyst is formed | |||
| Acetate | N-butyric acie | Acetate | N-butyric acie | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||||
| Catalyst H | 0.6 | 400 | 0.1 | 98.63 | 91.9 | 36.65 | 60.2 | 8.6 | 1∶1∶0.9 |
| 0.6 | 450 | 0.1 | 99.99 | 99.1 | 41.3 | 73.9 | 8.6 | 1∶1∶0.9 | |
Table 7
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | Butanone selectivity % | Catalyst is formed | |||
| Acetate | Propionic acid | Acetate | Propionic acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||||
| Catalyst H | 0.6 | 390 | 0.1 | 98.63 | 93.9 | 37.43 | 59.7 | 8.6 | 1∶1∶0.9 |
| 0.6 | 440 | 0.1 | 99.99 | 99.6 | 41.6 | 71.8 | 8.6 | 1∶1∶0.9 | |
Table 8
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | Methyln-hexyl ketone selectivity % | Catalyst is formed | |||
| Acetate | Positive enanthic acid | Acetate | Positive enanthic acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||||
| Catalyst H | 0.6 | 420 | 0.1 | 98.63 | 93.9 | 37.43 | 59.7 | 8.6 | 1∶1∶0.9 |
| 0.6 | 460 | 0.1 | 99.99 | 99.6 | 41.6 | 73.8 | 8.6 | 1∶1∶0.9 | |
Table 9
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | 3,3-dimethyl-2-butanone selectivity % | Catalyst is formed | |||
| Acetate | Pivalic acid | Acetate | Pivalic acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||||
| Catalyst H | 0.6 | 410 | 0.1 | 97.96 | 92.33. | 35.43 | 60.6 | 8.6 | 1∶1∶0.9 |
| 0.6 | 450 | 0.1 | 99.99 | 98.6 | 40.6 | 71.8 | 8.6 | 1∶1∶0.9 |
Table 10
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | 2-ten triketone selectivity % | Catalyst is formed | |||
| Acetate | Dodecoic acid | Acetate | Dodecoic acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium: cerium (mol ratio) | ||||
| Catalyst H | 0.6 | 420 | 0.1 | 97.96 | 81.33. | 35.43 | 51.6 | 8.6 | 1∶1∶0.9 |
| 0.6 | 470 | 0.1 | 99.99 | 91.6 | 35.6.6 | 70.1 | 8.6 | 1∶1∶0.9 | |
Table 11
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | Methyl isopropyl Ketone selectivity % | Catalyst is formed | ||
| Acetate | Isobutyric acid | Acetate | Isobutyric acid | Neodymia mass content % | ||||
| Catalyst A | 0.45 | 420 | 0.1 | 99.95 | 98.7 | 37.5 | 65.2 | 4.6 |
| 0.7 | 450 | 0.1 | 99.99 | 99.4 | 40.3 | 67.9 | 4.6 | |
Table 12 and patent EP085996 contrast
| Catalyst | Air speed h -1 | Reaction temperature ℃ | Reaction pressure MPa | Conversion ratio % | Methyl isopropyl Ketone selectivity % | Catalyst is formed | |||
| Acetate | Isobutyric acid | Acetate | Isobutyric acid | Total rare earth (TRE) mass content % | Neodymium: praseodymium (mol ratio) | ||||
| Catalyst A Right | 0.6 | 420 | 0.1 | 89.6 | 75.3. | 33.4 3 | 46.6 | 21.3 | 1∶1 |
| 0.6 | 460 | 0.1 | 91.5 | 86.3 | 35.6 6 | 62.1 | 21.3 | 1∶1 | |
| Catalyst B Right | 0.6 | 420 | 0.1 | 90.1 | 80.1 | 35.5 | 54.5 | 16.9 | 1∶1 |
| 0.6 | 460 | 0.1 | 95.4 | 91.5 | 37.2 9 | 63.99 | 16.9 | 1∶1 | |
| Catalyst C Right | 0.6 | 420 | 0.1 | 91.2 | 83.6 | 36.7 | 56.3 | 10.8 | 1∶1 |
| 0.6 | 460 | 0.1 | 96.7 | 93.6 | 38.3 9 | 64.5 | 10.8 | 1∶1 | |
Claims (12)
1. C
2-C
12The fat carboxylic acid ketonization catalyst is characterized in that catalyst is is carrier with the gama-alumina, and the mass percent of the gama-alumina in the carrier is 99.5-99.9%; Its active component is:
(A) oxide of lanthanum is as the monobasic active component, and its content is the 1-34% of catalyst quality; Or
(B) oxide of cerium is as the monobasic active component, and its content is the 5-35% of catalyst quality; Or
(C) oxide of praseodymium is as the monobasic active component, and its content is the 5-45% of catalyst quality; Or
(D) binary complex of the oxide of praseodymium, cerium is an active component, and its content is the 5-40% of catalyst quality, and wherein the mol ratio of praseodymium and cerium is 1: 0.1-30; Or
(E) binary complex of the oxide of neodymium, cerium is an active component, and its content is the 1-50% of catalyst quality, and wherein the mol ratio of neodymium and cerium is 0.1-30: 1; Or
(F) ternary complex of the oxide of cerium, praseodymium, neodymium is an active component, and its content is the 0.5-50% of catalyst quality, wherein praseodymium: neodymium: the mol ratio of cerium is 0.1-23: 0.1-30: 1-30.
2. according to the catalyst of claim 1, the specific area that it is characterized in that gama-alumina wherein is 120-350m
2/ g.
3. according to the catalyst of claim 1, the activating treatment method that it is characterized in that carrier wherein is that aqueous solution of nitric acid is washed method, roasting method or vacuum method.
4. according to the catalyst of claim 3, it is characterized in that aqueous solution of nitric acid wherein washes method for gama-alumina is carried out acidifying with 5-45% nitric acid, souring temperature is 5-65 ℃, acidificatoin time 0.5-48h is dried, bake out temperature 100-130 ℃, drying time is 2-60h, carry out roasting again, sintering temperature 450-700 ℃, roasting time is 2-8h.
5. according to the catalyst of claim 3, it is characterized in that wherein roasting method for gama-alumina is carried out roasting, sintering temperature 450-800 ℃, roasting time is 1-20h.
6. according to the catalyst of claim 3, it is characterized in that wherein vacuum method for gama-alumina is dried, bake out temperature 100-130 ℃, drying time is 2-60h, and vacuumizes.
7. according to the catalyst of claim 1, it is characterized in that Preparation of catalysts method wherein is the nitrate solution dipping of the carrier after will activating with active constituent, dip time is 1-60h, separates and soaks surplus liquid, carries out drying and high-temperature roasting, makes catalyst.
8. according to the catalyst of claim 1, it is characterized in that catalyst wherein is applied to C
2-C
12The fat carboxylic acid ketonization reaction generates C
3-C
13Aliphatic ketone.
9. catalyst according to Claim 8 is characterized in that C wherein
3-C
13Aliphatic ketone is the straight or branched aliphatic ketone.
10. catalyst according to Claim 8 is characterized in that ketonize reaction raw materials wherein is C
2-C
12The mixture of aliphatic carboxylic acid, acetate and water, C
2-C
12The mol ratio of aliphatic carboxylic acid, acetate and water is 0.8～2.0: 1.0～3.0: 2-5.
11. catalyst according to Claim 8 is characterized in that C wherein
3-C
13Aliphatic ketone is methyl isopropyl Ketone, 2 pentanone, butanone, methyln-hexyl ketone, 2-heptanone, 3,3-dimethyl-2-butanone or 2-ten triketones.
12. according to the catalyst of claim 10, it is characterized in that vapourizing temperature 120-350 ℃ of raw material wherein, the air speed of aliphatic carboxylic acid is 0.35-1.5h
-1, 350 ℃-500 ℃ of reaction temperatures, reaction unit is fixed bed reactors.
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| CNB2005101142570A CN100363098C (en) | 2005-10-25 | 2005-10-25 | Catalyst for C12-C12 fat carboxylic acid ketonization and its application |
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| CN104174397A (en) * | 2014-08-29 | 2014-12-03 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing acetone through gas phase catalytic ketonization of acetic acid and preparation method and application of catalyst |
| CN104193606A (en) * | 2014-09-28 | 2014-12-10 | 中国科学院山西煤炭化学研究所 | Technique for preparing acetone from synthetic gas |
| WO2020155145A1 (en) * | 2019-02-02 | 2020-08-06 | 中国科学院大连化学物理研究所 | Method for preparing ketone organics |
| CN113559843A (en) * | 2021-07-09 | 2021-10-29 | 江苏恒兴新材料科技股份有限公司 | Preparation method and application of catalyst for synthesizing 2-pentanone |
| US11267781B2 (en) | 2016-11-08 | 2022-03-08 | Rhodia Operations | Method for making end compounds from internal ketones issued from the decarboxylative ketonization of fatty acids or fatty acid derivatives |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4570021A (en) * | 1976-08-20 | 1986-02-11 | Sds Biotech Corporation | Preparation of ketones |
| US4528400A (en) * | 1976-08-20 | 1985-07-09 | Sds Biotech Corporation | Preparation of ketones |
| DE3709765A1 (en) * | 1987-03-25 | 1988-10-06 | Huels Chemische Werke Ag | METHOD FOR PRODUCING UNSYMMETRIC ALIPHATIC KETONES |
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| CN103058875A (en) * | 2013-01-23 | 2013-04-24 | 江西省奉新申新化工有限公司 | Process for synthesizing secondary carbon primary amine N1923 |
| CN104174397A (en) * | 2014-08-29 | 2014-12-03 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing acetone through gas phase catalytic ketonization of acetic acid and preparation method and application of catalyst |
| CN104174397B (en) * | 2014-08-29 | 2016-07-06 | 中国科学院山西煤炭化学研究所 | A kind of catalyst for acetic acid gas phase catalysis assimilation acetone and method for making and application |
| CN104193606A (en) * | 2014-09-28 | 2014-12-10 | 中国科学院山西煤炭化学研究所 | Technique for preparing acetone from synthetic gas |
| US11267781B2 (en) | 2016-11-08 | 2022-03-08 | Rhodia Operations | Method for making end compounds from internal ketones issued from the decarboxylative ketonization of fatty acids or fatty acid derivatives |
| WO2020155145A1 (en) * | 2019-02-02 | 2020-08-06 | 中国科学院大连化学物理研究所 | Method for preparing ketone organics |
| CN113559843A (en) * | 2021-07-09 | 2021-10-29 | 江苏恒兴新材料科技股份有限公司 | Preparation method and application of catalyst for synthesizing 2-pentanone |
| CN113559843B (en) * | 2021-07-09 | 2023-08-11 | 江苏恒兴新材料科技股份有限公司 | Preparation method and application of catalyst for synthesizing 2-pentanone |
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| CN100363098C (en) | 2008-01-23 |
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